Refractory metals are members of a group of elements that are difficult to isolate in pure form because of the stability of their compounds, such as oxides, chlorides, fluorides. Since the manufacturing of refractory metals is very complex, we will use tantalum extractive metallurgy as an example to illustrate the development of this technology.
State of the art tantalum powder production is based on the process of reducing potassium heptafluorotantalate (K2TaF7) with sodium (sodium reduction). The modern method for manufacturing tantalum was developed by Hellier and Martin1. A molten mixture of K2TaF7 and a diluent salt, typically NaCl, KF and/or KCl, is reduced with molten sodium in a stirred reactor. The manufacturing process requires the removal of the solid reaction products from the retort, separation of the tantalum powder from the salts by leaching with dilute mineral acid, and treatments like agglomeration and deoxidation to achieve specific physical and chemical properties. While the reduction of K2TaF7 with sodium has allowed the industry to make high performance, high quality tantalum powders primarily used in solid tantalum capacitor manufacturing, there are several drawbacks to this method. It is a batch process prone to the inherent variability in the system; as a result, batch-to-batch consistency is difficult. Using diluent salts adversely impacts the throughput. The removal of chlorides and fluorides in large quantities presents an environmental issue. Of fundamental significance, the process has evolved to a state of maturity such that a significant advance in the performance of the tantalum powder produced is unlikely. 1Hellier, E. G. and Martin, G. L., U.S. Pat. No. 2,950,185, 1960.
Over the years, numerous attempts were made to develop alternate ways for reducing tantalum compounds to the metallic state2,3,4,5,6. Among these was the use of active metals other than sodium, like calcium, magnesium, and aluminum and raw materials such as tantalum pentoxide and tantalum chloride.
Konig et al. 6developed a vertical device for producing finely-divided metal powders (Ta, Nb, W, Zr, etc.) and metal compounds (TiN, TiC, Nb2O5) by reducing the corresponding metal chloride with hydrogen, methane, or ammonia. While this technique allows continuous production, the generation of large quantities of hydrochloric acid presents serious corrosion and environmental problems. The chlorides are very hydroscopic and, therefore, require special handling with an inert and dry atmosphere. In addition, some of the metal chlorides are very expensive. 2Marden, J. W., U.S. Pat. No. 1,602,542, 1926.3Marden, J. W. and Rich, M. H., U.S. Pat. No. 1,728,941, 1927.4Gardner, D., U.S. Pat. No. 2,516,863, 1946.5Restelli, A., U.S. Pat. No. 3,647,420, 1972.6König, T., et al., U.S. Pat. No. 5,356,120, 1994.
Kametani et al. 7developed a process for reducing gaseous titanium tetrachloride with atomized molten magnesium or sodium in a vertical type reactor in the temperature range of 650-900° C. Though the reaction was very exothermic, it was not self-sustaining due to a special effort designed to avoid the formation of titanium-iron intermetallic compounds at high temperatures (the melting point of Fe—Ti eutectic is 1080° C.). 7Kametani, H., Sakai, H., GB Patent 2231883, 1990
Marden,2 Gohin and Hivert,8 Hivert and Tacvorian9 suggested the use of gaseous magnesium to better control the process parameters. The gaseous reducing agent was generated in-situ from a mixture of metal oxide and reducing agent or outside the reactor enclosure. They managed to produce at bench scale fine zirconium, titanium, tungsten, molybdenum, and chromium powders. The method was of batch type. The only controlled parameter was the magnesium (calcium) partial pressure. The kinetics and the temperature of the charge were a function of the gaseous magnesium (calcium) flow rate and were impossible to control due to the condensation of magnesium (calcium) on the cold parts of the reactor. Since both melting and evaporation of Mg (Ca) without condensation on the cold parts was practically impossible, the process had to be periodically stopped for the removal of the build-up. Therefore, continuous operation could not be carried out. 2Marden, J. W., U.S. Pat. No. 1,602,542, 1926.8Gohin, G. M., Hivert, A. R., U.S. Pat. No. 3,658,507, 1972.9Hivert, A. R., Tacvorian, S., U.S. Pat. No. 2,881,067, 1959.
Our own experience has been that the production and transport to the reaction zone of a gaseous metal like magnesium is extremely difficult. The metal will condense at any cold spot in the transfer plumbing to form a plug. The metal attacks the container to degrade its integrity over time creating a significant maintenance problem. Control of the reducing agent stoichiometry in the reaction zone is difficult, as it requires maintaining a measured flow rate of a gaseous metal/carrier gas (argon) mixture of known composition into the reactor.
Restelli5 developed a process for producing niobium and tantalum powders by the reduction of the corresponding oxides with carbon in vacuum. Since the Gibbs Free Energy for the carbothermic reduction reaction of Ta2O5 becomes negative at approximately 1500° C., the reaction requires high temperature, and particle sintering occurs, thus reducing the surface area of the powder. Another significant drawback of the proposed technology was contamination of the metal powders with carbon, making it very difficult to use them for capacitor manufacturing. 5Restelli, A., U.S. Pat. No. 3,647,420, 1972.
Numerous attempts were made to produce tantalum and niobium powders by metalothermic reduction of their oxides with Mg, Al, Ca in a bomb type reactor.3,4 A blend of finely-divided oxide and metal reducing agent was placed into a reactor and then ignited. The temperature could not be controlled and therefore it was not possible to achieve reproducible physical and chemical properties of the metal powders. The residual Mg (Al, Ca) content was high due to the formation of tantalates and niobates. The process was found to be unsuitable for manufacturing high quality capacitor grade powders. 3Marden, J. W. and Rich, M. H., U.S. Pat. No. 1,728,941, 1927.4Gardner, D., U.S. Pat. No. 2,516,863, 1946.
Shekhter et al.10 described a method for controlled reduction of tantalum and niobium oxide with gaseous magnesium to produce capacitor grade tantalum and niobium powders (batch magnesium reduction). The key is control of the reaction process to achieve essentially isothermal conditions. The batch magnesium reduction process requires excess amount of magnesium to compensate for its condensation on the cold parts of the furnace. 10Shekhter, L., Tripp, T., Lanin, L., U.S. Pat. No. 6,171,363, 2001
It is a principle object of the present invention to provide a new process for producing high performance, high quality tantalum, niobium, and other refractory metals and blends or alloys thereof by reducing solid/liquid metal oxides in a steady, self-sustaining reaction zone, thereby eliminating one or more, preferably all of the problems associated with the traditional double salt reduction and other processes described above.
It is a further object of the invention to provide a controlled, continuous production method of reduction.
It is a further object of the present invention to provide a reduction method that produces a high quality refractory metal by eliminating halide by-products and carbon contamination.
It is a further object of the invention to provide improved metal forms.
It is a further object of the invention to provide a metal powder having an improved uniform morphology.